Process of refining viscous petroleum oils



R. W. HANNA.

Patented Jan. 24, 1922.

2 SHhETS-SHEET 1.

PROCESS OF REFINING VISCOUS PETROLEUM OILS.

APPLICATION FlLED JAN. 13, 1920. 1,404,889.

j with do m j K231 i Eta M HL R. W. HANNA.

PROCESS OF REFINING VISCOUS PETROLEUM OILS.

APPLICATION HLED JAN. 13. I920.

1,404,3 9, Patented Jan. 24,1922.

2 SHHiTS-SHEET 2.

UNITED STATES PATENT OFFl CE.

RICHARD W. HANNA, 0F RICHMOND, CALIFORNIA, ASSIGNOR TO STANDARD OIL company or cuaroaum, or am or'cmroame.

FRANCISCO, CALIFORNIA, A CORPORATION PROCESS OI REFINING VISCOUS FETROLEUM OILS.

Specification of Letters Patent.

Application filed January 13, 1920. Serial No. 351,100.

. carbocyclic series, for the manufacture of the resultant sludge.

lubricating oils.

My invention relates to a practically continuous process of purifying and refining California petrbleum viscous distillates for the manufacture of lubricating oils, in which I remove from said viscous distillates, by means of sulphuric acid and other refining li uids, certain hydrocarbons which contain sdiphur in chemical combination, certain hydrocarbons which contain nitrogen in chemical combination, certain asphaltic hydrocarbons, and certain unsaturated hydrocarbons.

An object of my invention is to provide a continuous time saving method of refining.

Another object of my invention is to provide a process for commingling viscous hydrocarbons with sulphuric acid and preventing oxidation which increases with the heat of reaction, thus preservin the color and increasing the quantity of the yields.

Another object of my invention is to extract the heat of reaction'produced upon the comm-ingling of viscous hydrocarbons with sulphuric acid, to prevent the reduction of Another object of my invention is to pro vide a method or process whereby viscous hydrocarbons may be commingled with sulphuric acid or other refining agents, 'without the use of air agitation, paddles, or similar means. a

A further object of my invention is'to' providea process of the kind referred to, which will utilize temperature control and the exclusion of air tov prevent oxidation products from being formed.

invented a l of which the following lS acid is added other-bodies commonly known as system directly after A further object is to provide a continu-- ous means of collecting the products formed It has heretofore been customary to treat that fraction of oil obtained in the distillation of crude petroleum oil, which fraction is commonly known as lubricating distillate or lubricating reduced distillate, with sulph quantities and of such strength-as may be necesary to obtain the desired color and grade. This treatment 1s usually carried out in tanks called agitators, where the required amount of sulphuric brought into contact with the 011 by air agitatlon. The sulphuric acid reacts on the oil, forming sulpho-acids and slud with the liberation of heat.

I have discovered that the liberation of heat during the aforesaid action of the sulphuric acid on the oil, promotes oxidation. art1cularly 1s this so in the presence of air. Such oxidation is accompanied by the for mat1on of petroleum carboxyl-acids, phenolic h drocarbons and carbo-xyl-sulpho acids, w ich are soluble in the oil and act as an emulslfymg agent in the neutralizing and washing step hereafter described. I at- Patented Jan.'24, 1922.

tribute this oxidation partly to the air agitatlon employed in the aforesaid agitation and partly to the fact that .the action of the sulphuric acid on the oil takes place while the products are in a heated condititon due to the heat of reaction bet-ween the oil and acid. The sulphuric acid reacting on the oil iirheated condition is partly reduced to sulphurous acid intensifying the formation Qf emulsifying or coloring bodies.

y invention provides a continuous conducting away of the main heat of reaction produced in the reaction of the acid on the oil, and the prevention of air coming into contact with the oil under tratment, thus eliminating the formation of emulsifying agents.

My invention further pnovides for the continuous introduction of a small amount of water (2% to 6% by volume) into the the acid treatment,

which causes the small particles of sulphoacids or sludge to coalesce and settle.

With the processes as practiced heretofore it has been customary to treat the oil in tanks, after drawing off the acid sludge or en] ho-acids, with a water solution of caustic sod; in suflicient quantity to neutralize all the acids present, after which the oil is washed with hot water'to remove all traces of caustic sfoda laiidfsodium salts. 2111c todthe resence o em s1 ing a ts'pr uce in such rocesses as'aforesaidf this treating or washing of the oil has been accomplished by a loss of treated oil as high as M process contemplates a like treat ng of the oil with a solution of caustic soda after separating the sulpho-acids or sludge. This ma be performed in a continuous manner similar to the acid treating rocess, and owing to the absence of emu slfymg agents the loss in treatment 1s greatly reduced.

In the-accompanying drawings:

Figure 1 is a general diagrammatic view of an apparatus in which my lnventlon may be carried out.

Fi 2 illustrates one form of mixer which ma e used for commingling vlscous 011s wit sulphuric acid.

-' a pipe which is connected to the line 6 Fig. 3 illustrates another form of such mixer.

Fig.4 illustrates another form of the same.

Fig. 5 illustrates another form of the same.

Fig. 6 illustrates another form of the same.

Fig. 7 illustrates one. form of union between the oil line and the acid line.

Referring to Fig. 1 of the drawings 1 designates a storage tank for the oil .to be treated. A pi e 2 connects the tank 1 to the suction si e of a pump 3, which dis g' charges into a pipe 4. The pipe 4 is connected to an orifice meter5 which records the rate of flow. From the orifice meter 5 the oil to be treated passes into a' ipe 6, where it meets the incoming acid om bymeans ofaTor Y.

17 is a tank for acid connected to a pipe 18. The pi e 18 is connected to an orifice meter 19, w ich latter is connected to the pi e 20 by the Y or T into the line 6.

he line 6 is connected to a mixer 7 which is in turn coupled by means of a pipe 8 with a second mixer 9. The mixers 7 and 9 are surrounded by a water jacket 21.

The mixer 9 is connected to a pump 11- b means of a pipe 10. The pump 11 discharges into a pipe 13. A water line 12 'leads from a source of water and connects with the pipe 13. An orifice meter 22 is positioned on the pipe 12 to determine and regulate the flow of water into the pipe 13.

- chemica carried out in this process as follows:

The oil to be treated may range in is cosity from as low as seconds at 100 Fahr. to as high at 250 seconds at 210 Fahn, when taken with the Saybolt viscosimeter.

From tank 1 the oil to be treated enters the suction side of pump 3 by means of pipe 2. The pump 3 discharges through pipe 4 into orifice meter 5 which records the flow of oil. From orifice meter 5 the oil to be treated flows into the line 6 whereit is mixed continuously with the required regulated quantity of acid from pipe 20.

17 is a tank or blow case, which can be filled with acid by pipe 24, which leads to a source of acid. 23 is a pipe leading to a source of compressed air. 25 is 9.. pi e by means of which the pressure can be re eased into the air when it is necessaryto fillthe tank 17 with acid.

A pressure of to 150 pounds per square inch absolute is kept on tank 17, which causes the acid to flow through line 18 into orifice meter and regulator 19. Orifice meter 19 is controlled by means of valves so that the flow of acid can beregulated.

From the ipe 6, the oil to be treated mixed with t e required amount of acid, passes through mixers 7 and 9. Y

The mixers 7 and 9 may be conveniently constructed in any of the forms illustrated in Figs. 2-6 inclusive. In Fig. 2 the mixer comprises a plurality of circular plates 26 which are perforated on alternate half sections as shown at 27. In Fig. 3 the mixer comprises a perforated cap 28. 'In- Fig. 4 the mixer com rises a perforated plate 29 arranged slight y different from that of Fig. 3. In- Fig. 5 the mixer comprises a plurality of rectangular plates 30 erforated alternately. n Fig. 6 the mixer comprises a plurality of return bends 31.

In the mixers 7 and 9, the oil and acid are commin led. The heat produced by the reaction between the oil and the acid isconducted awa as fast as it islib erated by means of co d water which flows through the water 'acket 21.

From mixer 9 t e acid treated oil and acid sludge pass through the pipe 10 into the suction side of pump 11, which" discharges into line 13. 11 line 13, the treated oil mixed with the acid sludge or sulphoacids. produced by the treatment are mixed with a small quantity of water 2% to 6% by volume, by means of line 12, controlled by watermeter and regulator 22.

treated oil can be separated in tank 16, the acid sludge forming a lower layer. This introduction of water also is attended by the liberation of heat, which is conducted away by any suitable means, not shown, as the oil passes through the cooler 14.

Cooler 14 is connected to a settling tank 16, where the acid sludge settles to the bottom forming a lower layer and is drawn 011.

The treated oil is then neutralized with a water solution of caustic soda washed with water, and finished by well known methods, or the apparatus here described can be used for this neutralizing and washing steps.

I claim:

1. The continuous process of treating viscous petroleum distillate with sulphuric acid which comprises forcing together the oil and acid under pressure in the absence of air in a conduit and conducting away the heat of the reaction from the intermingled oil and acid as generated.

2. The continuous process of treating viscous petroleum distillate with sulphuric acid which comprises forcing together the oil and acid under pressure into a conduit and in the absence of air, and conductin away the heat of the reactions as the same is liberated during the passage of the oil and acid through said conduit.

Signed at Richmond, California, this 2nd day of January, 1920.

RICHARD W. HANNA.

Witnesses:

H. M. FLINT, W. D. Mason. 

